Hair care compositions comprising malodor reduction compositions

ABSTRACT

The present invention relates to hair care compositions comprising malodor reduction compositions and methods of using such hair care compositions. Such hair care compositions comprising the malodor control technologies disclosed herein provide malodor control without leaving an undesirable scent and when perfume is used to scent such compositions, such scent is not unduly altered by the malodor control technology.

FIELD OF THE INVENTION

The present invention relates to hair care compositions comprisingmalodor reduction compositions and methods of making and using such haircare compositions.

BACKGROUND OF THE INVENTION

Unscented or lightly scented products are desired by consumers as theymay be considered more natural and discreet than more highly scentedproducts. Manufacturers of unscented or lightly scented products forcontrolling malodors rely on malodor reduction ingredients or othertechnologies (e.g. filters) to reduce malodors. However, effectivelycontrolling malodors, for example, amine-based malodors (e.g. fish andurine), thiol and sulfide-based malodors (e.g. garlic and onion), C₂-C₁₂carboxylic acid based malodors (e.g. body and pet odor), indole basedmalodors (e.g. fecal and bad breath), short chain fatty aldehyde basedmalodors (e.g. grease) and geosmin based malodors (e.g. mold/mildew) maybe difficult, and the time required for a product to noticeably reducemalodors may create consumer doubt as to the product's efficacy onmalodors. Often times, manufacturers incorporate scented perfumes tohelp mask these difficult malodors.

Unfortunately, malodor control technologies typically cover up themalodor with a stronger scent and thus interfere with the scent of theperfumed or unperfumed situs that is treated with the malodor controltechnology. Thus, limited nature of the current malodor controltechnologies is extremely constraining. Thus what is needed is a broaderpalette of malodor control technologies so the perfume community candeliver the desired level of character in a greater number ofsituations/applications. Surprisingly, Applicants recognized that inaddition to blocking a malodor's access to a sensory cell, in order toachieve the desired goal, a malodor control technology must leave suchsensor cell open to other molecules, for example scent molecules. Thus,hair care compositions comprising the malodor control technologiesdisclosed herein provide malodor control without leaving an undesirablescent and, when perfume is used to scent such compositions, such scentis not unduly altered by the malodor control technology.

Selenium sulfide containing anti-fungal hair and scalp care compositionsprovide some of the most effective protection from and relief ofdandruff conditions. Historically, selenium sulfide and othersulfur-based formulations are highly medicinal and pungent smelling—bothin use and throughout the day—due to residual sulfur compounds depositedon the hair and scalp. These significant negative cosmetic attributesmay cause consumers to avoid selenium sulfide and other sulfur-basedformulations and therefore product usage compliance is difficult and asa result consumers often do not find complete relief from their dandruffcondition.

SUMMARY OF THE INVENTION

The present invention relates a hair care composition comprising, basedon total composition weight: a sum total of from about 0.0001% to about2% of alpha,alpha,6,6-tetramethylbicyclo[3.1.1]hept-2-ene-propanal) andone or more malodor reduction materials having a Sulfur MORV>3; fromabout 0.01% to about 10% of a scalp active material selected from thegroup consisting of selenium sulfide, sulfur and mixtures thereof; fromabout 0.1% to about 40%, of a surfactant.

DETAILED DESCRIPTION OF THE INVENTION Definitions

“Hair Care” composition” as defined herein, may include shampoos,conditioners and leave-on-treatments.

“Rinse-off” means the intended product usage includes application tohair followed by rinsing and/or wiping the product from the skin and/orhair within a few seconds to minutes of the application step.

“STnS” refers to sodium trideceth(n) sulfate, wherein n can define theaverage number of moles of ethoxylate per molecule.

As used herein “MORV” is the calculated malodor reduction value for asubject material. A material's MORV indicates such material's ability todecrease or even eliminate the perception of one or more malodors. Forpurposes of the present application, a material's MORV is calculated inaccordance with method found in the test methods section of the presentapplication.

As used herein, “malodor” refers to compounds generally offensive orunpleasant to most people, such as the complex odors associated withbowel movements.

As used herein, “odor blocking” refers to the ability of a compound toreduce the perception of a malodor.

As used herein, the term “perfume” does not include malodor reductionmaterials. Thus, the perfume portion of a composition does not include,when determining the perfume's composition, any malodor reductionmaterials found in the composition as such malodor reduction materialsare described herein. In short, if a material has a malodor reductionvalue “MORV” that is within the range of the MORV recited in the subjectclaim, such material is a malodor reduction material for purposes ofsuch claim.

As used herein, the terms “a” and “an” mean “at least one”.

As used herein, the terms “include”, “includes” and “including” aremeant to be non-limiting.

Unless otherwise noted, all component or composition levels are inreference to the active portion of that component or composition, andare exclusive of impurities, for example, residual solvents orby-products, which may be present in commercially available sources ofsuch components or compositions.

All percentages and ratios are calculated by weight unless otherwiseindicated. All percentages and ratios are calculated based on the totalcomposition unless otherwise indicated.

It should be understood that every maximum numerical limitation giventhroughout this specification includes every lower numerical limitation,as if such lower numerical limitations were expressly written herein.Every minimum numerical limitation given throughout this specificationwill include every higher numerical limitation, as if such highernumerical limitations were expressly written herein. Every numericalrange given throughout this specification will include every narrowernumerical range that falls within such broader numerical range, as ifsuch narrower numerical ranges were all expressly written herein.

Hair Care Compositions

Rinse-off hair care compositions can come in a variety of forms. Forexample, a hair care composition can be in a liquid form and can be ashampoo, conditioning shampoo, Hair Care compositions can includeperfume materials. Many consumers prefer hair care compositions that canconsistently provide a desired scent, or odor that can be perceived eachtime the product is used. Perfume materials can provide the desiredscent or odor to these hair care compositions. These perfume (i.e.,fragrance) materials can include perfumes, perfume raw materials, andperfume delivery systems.

Malodor Reduction Materials

A non-limiting set of suitable malodor reduction materials are providedin the tables below.

TABLE 1 List of materials with Sulfur MORV > 3 Octanol/Water PartitionACD Room Coefficient, Malodor Temp (25 C.) logP (ACD, Reduction: VaporPressure Consensus Log (1/EC0) (mm Hg, ACD, algorithm, 3-methyl-3- CASEXP-14- EXP-14- sulfanylhexan-1-ol Number Number Name AA6010-003)AA6010-002) (3M3S1H) 188199-50-0 2′-isopropyl-1,7,7- 2.3E−02 4.30 3.04trimethylspiro[bicyclo[2.2.1]heptane-2,4′- [1,3]dioxane] 154171-77-4(1′,1′,5′,5′- 1.5E−02 4.51 4.66 tetramethylhexahydro-2′H,5′H-spiro[[1,3]dioxolane-2,8′- [2,4a]methanonaphthalene] K 5413-60-53a,4,5,6,7,7a-hexahydro-1H-4,7- 1.4E−02 2.79 3.44 methanoinden-6-ylacetate) 68480-11-5 Decahydro-3H-spiro[furan-2,5′- 1.4E−02 3.36 3.22[4,7]methanoindene] 19870-74-7 CEDRYL METHYL ETHER 1.3E−02 5.08 5.52116126-82-0 Ethyl (1R,2R,3R,4R)-3- 1.2E−02 3.68 3.22isopropylbicyclo[2.2.1]hept-5- ene-2-carboxylate 3738-00-93aR,5aR,9aR,9bR)-3a,6,6,9a- 9.3E−03 5.11 3.06tetramethyldodecahydronaphtho[2,1-b]furan 33885-52-8alpha,alpha,6,6-tetramethyl 6.9E−03 4.31 3.18 bicyclo[3.1.1]hept-2-ene-propanal 1139-30-6 4,5-epoxy-4,11,11-trimethyl-8- 6.7E−03 4.47 3.57methylenebicyclo(7.2.0)undecane) 41724-19-0 4aR,8aS)-7-methyloctahydro-6.5E−03 2.66 3.43 1,4-methanonaphthalen-6(2H)- one 86803-90-95-methoxyoctahydro-1H-4,7- 4.4E−03 2.08 3.87methanoindene-2-carbaldehyde 68738-96-5 8,8-dimethyl-6,7-dihydro-5H-4.4E−03 3.92 3.11 naphthalene-2-carbaldehyde 41816-03-92R,4a′R,8a′R)-3,7′-dimethyl- 3.3E−03 3.09 3.573′,4′,4a′,5′,8′,8a′-hexahydro- 1′H-spiro[oxirane-2,2′-[1,4]methanonaphthalene]) 476332-65-7 (2,2,6,6,7,8,8- 3.2E−03 6.14 5.66heptamethyldecahydro-2H- indeno[4,5-b]furan 23787-90-81,3,4,6,7,8alpha-hexahydro- 2.6E−03 4.09 4.531,1,5,5-tetramethyl-2H-2,4alpha- methanophtalen-8(5H)-one) 67634-20-23a,4,5,6,7,7a-hexahydro-1H-4,7- 2.4E−03 3.51 4.13 methanoinden-5-ylisobutyrate 57345-19-4 3S,5aR,7aS,11aS,11bR)- 2.0E−03 5.18 4.973,8,8,11a- tetramethyldodecahydro-5H- 3,5a-epoxynaphtho[2,1-c]oxepine68912-13-0 (8,8-dimethyl-3a,4,5,6,7,7a- 1.8E−03 4.00 5.04hexahydro-1H-4,7- methanoinden-6-yl propionate) 211299-54-64aR,5R,7aS,9R)-2,2,5,8,8,9a- 1.8E−03 4.85 6.82hexamethyloctahydro-4H-4a,9- methanoazuleno[5,6- d][1,3]dioxole68901-32-6 2-(8-isopropyl-6- 1.2E−03 3.81 3.04methylbicyclo[2.2.2]oct-5-en-2- yl)-1,3-dioxolane 68039-44-13a,4,5,6,7,7a-hexahydro-1H-4,7- 1.2E−03 3.96 3.79 methanoinden-6-ylpivalate 823178-41-2 3a,5,6,7,8,8b-hexahydro- 7.4E−04 4.97 5.242,2,6,6,7,8,8-heptamethyl-4H- indeno(4,5-d)-1,3-dioxole 39900-38-4(3R-(3alpha, 6.3E−04 4.97 4.83 3a,6alpha,7,8aalpha))-octahydro-3,6,8,8-tetramethyl-1H-3a,7- methanoazulen-6-yl formate 77-53-2(1S,2R,5S,7R,8R)-2,6,6,8- 5.7E−04 4.49 4.40tetramethyltricyclo[5.3.1.01,5]undecan-8-ol 54464-57-21-((2S,3S)-2,3,8,8-tetramethyl- 5.4E−04 4.72 3.26 1,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)ethan- 1-one 30168-23-1((E)-4-((3aS,7aS)-octahydro-5H- 4.4E−04 3.97 4.42 4,7-methanoinden-5-ylidene)butanal 5986-55-0 1R-(1alpha,4beta, 2.8E−04 4.46 4.344aalpha,6beta,8aalpha))- octahydro-4,8a,9,9-tetramethyl-1,6-methano-1(2H)-naphthol 32214-91-8 [(3Z)-4,11,11-trimethyl-8- 2.5E−045.50 3.55 methylidene-5- bicyclo[7.2.0]undec-3-enyl] acetate 552-02-3(1aR,4S,4aS,7R,7aS,7bS)- 1.8E−04 4.72 4.12 1,1,4,7-tetramethyldecahydro-1H-cyclopropa[e]azulen-4-ol 69486-14-2 Z)-6-ethylideneoctahydro-2H-1.1E−04 2.32 3.82 5,8-methanochromen-2-one) 32388-55-91-((3R,3aR,7R,8aS)-3,6,8,8- 8.5E−05 4.97 4.49 tetramethyl-2,3,4,7,8,8a-hexahydro-1H-3a,7- methanoazulen-5-yl)ethan-1-one 167254-80-03,5,5,6,7,8,8-heptamethyl- 6.9E−05 5.88 3.365,6,7,8-tetrahydronaphthalene-2- carbonitrile 66072-32-04-(1,7,7-trimethyl-6- 3.0E−05 4.45 3.50bicyclo[2.2.1]heptanyl)cyclohexan-1-ol 501929-47-1(E)-4-((3aR,4R,7R,7aR)- 8.5E−06 3.87 5.441,3a,4,6,7,7a-hexahydro-5H-4,7- methanoinden-5-ylidene)-3-methylbutan-2-ol 3681-73-0 (E)-3,7-dimethylocta-2,6-dien-1- 3.0E−0910.75 3.31 yl palmitate)

TABLE 2 List of materials with Sulfur MORV > 3; ClogP > 3 and VP > .005Octanol/Water Partition ACD Room Coefficient, Malodor Temp (25 C.) logP(ACD, Reduction: Vapor Pressure Consensus Log (1/EC0) (mm Hg, ACD,algorithm, 3-methyl-3- CAS EXP-14- EXP-14- sulfanylhexan-1-ol NumberMaterial Name Number AA6010-003) AA6010-002) (3M3S1H) 12′-isopropyl-1,7,7- 188199-50-0 2.3E−02 4.30 3.04trimethylspiro[bicyclo[2.2.1]heptane- 2,4′-[1,3]dioxane 2 (1′,1′,5′,5′-154171-77-4 1.5E−02 4.51 4.66 tetramethylhexahydro-2′H,5′H-spiro[[1,3]dioxolane-2,8′- [2,4a]methanonaphthalene] K 3SPIRO[FURAN-2(3H),5′-(4,7- 68480-11-5 1.4E−02 3.36 3.22METHANO-5H-INDENE], DECAHYDRO 4 (3R,3aR,6S,7S,8aS)-6- 19870-74-7 1.3E−025.08 5.52 methoxy-3,6,8,8- tetramethyloctahydro-1H-3a,7- methanoazulene5 Ethyl (1R,2R,3R,4R)-3- 116126-82-0 1.2E−02 3.68 3.22isopropylbicyclo[2.2.1]hept-5- ene-2-carboxylate 63aR,5aR,9aR,9bR)-3a,6,6,9a- 3738-00-9 9.3E−03 5.11 3.06tetramethyldodecahydronaphtho[2,1-b]furan 7 (alpha,alpha,6,6-tetramethyl33885-52-8 6.9E−03 4.31 3.18 bicyclo[3.1.1]hept-2-ene- propanal) 84,5-epoxy-4,11,11-trimethyl-8- 1139-30-6 6.7E−03 4.47 3.57methylenebicyclo(7.2.0)undecane) 9 2′-isopropyl-1,7,7- 188199-50-02.3E−02 4.30 3.04 trimethylspiro[bicyclo[2.2.1]heptane-2,4′-[1,3]dioxane

TABLE 3 Sulfor MORV > 3 and ClogP > 3 11 1,3,4,6,7,8alpha-hexahydro-23787-90-8 2.6E−03 4.09 4.53 1,1,5,5-tetramethyl-2H-2,4alpha-methanophtalen- 8(5H)-one) 12 8,8-dimethyl-3a,4,5,6,7,7a-68912-13-0 1.8E−03 4.00 5.04 hexahydro-1H-4,7- methanoinden-6-ylpropionate) 13 2-(8-isopropyl-6- 68901-32-6 1.2E−03 3.81 3.04methylbicyclo[2.2.2]oct-5-en-2- yl)-1,3-dioxolane 14[(3Z)-4,11,11-trimethyl-8- 32214-91-8 2.5E−04 5.50 3.55 methylidene-5-bicyclo[7.2.0]undec-3-enyl] acetate (E)-3,7-dimethylocta-2,6-dien-3681-73-0 3.0E−09 10.75 3.31 1-yl palmitate)The materials in Tables 1-3 may be supplied by one or more, but notlimited to, the following: Firmenich Inc. of Plainsboro N.J. USA;International Flavor and Fragrance Inc. New York, N.Y. USA; TakasagoCorp. Teterboro, N.J. USA; Symrise Inc. Teterboro, N.J. USA;Sigma-Aldrich/SAFC Inc. Carlsbad, Calif. USA; and Bedoukian ResearchInc. Danbury, Conn. USA.

In one aspect of said hair care composition, said composition comprisesone or more perfume raw materials.

In one aspect of said hair care composition, said composition comprisesa total of, based on total consumer product weight, from about 0.1% toabout 7% of one or more of said malodor reduction materials and fromabout 3% to 30% of a surfactant, and, optionally, a miscellar phaseand/or lamellar phase.

In one aspect of said hair care composition, said composition comprisesa total, based on total consumer product weight, of from about 0.1% toabout 50% of a material selected from structurants, humectants, fattyacids, inorganic salts, antimicrobial agents, antimicrobial agentsactives and mixtures thereof.

In one aspect of said hair care composition, said composition comprisesan adjunct ingredient selected from the group consisting of clay mineralpowders, pearl pigments, organic powders, emulsifiers, distributingagents, pharmaceutical active, topical active, preservatives,surfactants and mixtures thereof.

A method of controlling malodors comprising: contacting a situscomprising a malodor and/or a situs that will become malodorous with ahair care composition selected from the group consisting of the haircare compositions disclosed herein is disclosed.

In one aspect of said method, said situs comprises the head of hair andsaid contacting step comprises contacting said hair containing a malodorwith a sufficient amount of present invention's hair care composition toprovide said hair with a level of malodor reduction material at least0.0001 mg of malodor reduction material per body or head of hair, in anembodiment from about 0.0001 mg of malodor reduction material per headof hair to about 1 mg of malodor reduction material per head of hair, ina further embodiment from about 0.001 mg of malodor reduction materialper head of hair about 0.5 mg of malodor reduction material per body orhead of hair, a further embodiment from about 0.01 of malodor reductionmaterial per head of hair to about 0.2 mg of malodor reduction materialper head of hair.

Adjunct Materials

While not essential for the purposes of the present invention, thenon-limiting list of adjuncts illustrated hereinafter are suitable foruse in the instant compositions and may be desirably incorporated incertain aspects of the invention, for example to assist or enhanceperformance,

A variety of optional ingredients can also be added to hair carecompositions. Optional ingredients can include, but are not limited to,structurants, humectants, fatty acids, inorganic salts, and otherantimicrobial agents or actives.

A hair care composition can also include hydrophilic structurants suchas carbohydrate structurants and gums. Some suitable carbohydratestructurants include raw starch (corn, rice, potato, wheat, and thelike) and pregelatinized starch. Some suitable gums include carregeenanand xanthan gum. A hair care composition can include from about 0.1% toabout 30%, from about 2% to about 25%, or from about 4% to about 20%, byweight of the hair care composition, of a carbohydrate structurant.

A hair care composition can also include one or more humectants.Examples of such humectants can include polyhydric alcohols. Further,humectants such as glycerin can be included the hair care composition asa result of production or as an additional ingredient. For example,glycerin can be a by-product after saponification of the hair carecomposition. Including additional humectant can result in a number ofbenefits such as improvement in hardness of the hair care composition,decreased water activity of the hair care composition, and reduction ofa weight loss rate of the hair care composition over time due to waterevaporation.

A hair care composition can include inorganic salts. Inorganic salts canhelp to maintain a particular water content or level of the hair carecomposition and improve hardness of the hair care composition. Theinorganic salts can also help to bind the water in the hair carecomposition to prevent water loss by evaporation or other means. A haircare composition can optionally include from about 0.01% to about 15%,from about 1% to about 12%, or from about 2.5% to about 10.5%, by weightof the hair care composition, of inorganic salt. Examples of suitableinorganic salts can include magnesium nitrate, trimagnesium phosphate,calcium chloride, sodium carbonate, sodium aluminum sulfate, disodiumphosphate, sodium polymetaphosphate, sodium magnesium succinate, sodiumtripolyphosphate, aluminum sulfate, aluminum chloride, aluminumchlorohydrate, aluminum-zirconium trichlorohydrate, aluminum-zirconiumtrichlorohydrate glycine complex, zinc sulfate, ammonium chloride,ammonium phosphate, calcium acetate, calcium nitrate, calcium phosphate,calcium sulfate, ferric sulfate, magnesium chloride, magnesium sulfate,and tetrasodium pyrophosphate.

A hair care composition can include one or more additional antibacterialagents that can serve to further enhance antimicrobial effectiveness ofthe hair care composition. A hair care composition can include, forexample, from about 0.001% to about 2%, from about 0.01% to about 1.5%,or from about 0.1% to about 1%, by weight of the hair care composition,of additional antibacterial agent(s). Examples of suitable antibacterialagents can include carbanilides, triclocarban (also known astrichlorocarbanilide), triclosan, a halogenated diphenylether availableas DP-300 from Ciba-Geigy, hexachlorophene,3,4,5-tribromosalicylanilide, and salts of 2-pyridinethiol-1-oxide,salicylic acid, and other organic acids. Other suitable antibacterialagents are described in U.S. Pat. No. 6,488,943.

Scalp Active Material

In an embodiment of the present invention, the hair care composition maycomprise a scalp active material, which may be an anti-dandruff active.In an embodiment, the anti-dandruff active is selected from the groupconsisting of: pyridinethione salts; zinc carbonate; azoles, such asketoconazole, econazole, and elubiol; selenium sulfide; particulatesulfur; keratolytic agents such as salicylic acid; and mixtures thereof.In a further embodiment, the anti-dandruff active may be ananti-dandruff particulate. In an embodiment, the anti-dandruffparticulate is a pyridinethione salt. Such anti-dandruff particulateshould be physically and chemically compatible with the components ofthe composition, and should not otherwise unduly impair productstability, aesthetics or performance.

In an embodiment of the present invention, the selenium sulfide ispresent from about about 0.01% to about 10%, in an embodiment from about0.1% to about 8%, in a further embodiment, from about 1% to about 5%.

In an embodiment of the present invention, the sulfur is present fromabout 0.01% to about 10%, in an embodiment from about 0.1% to about 8%,in a further embodiment, from about 1% to about 5% and from about 2% toabout 5%.

Pyridinethione particulates are suitable particulate anti-dandruffactives for use in composition of the present invention. In anembodiment, the anti-dandruff active is a 1-hydroxy-2-pyridinethionesalt and is in particulate form. In an embodiment, the concentration ofpyridinethione anti-dandruff particulate ranges from about 0.01% toabout 5%, by weight of the composition, or from about 0.1% to about 3%,or from about 0.1% to about 2%. In an embodiment, the pyridinethionesalts are those formed from heavy metals such as zinc, tin, cadmium,magnesium, aluminium and zirconium, generally zinc, typically the zincsalt of 1-hydroxy-2-pyridinethione (known as “zinc pyridinethione” or“ZPT”; zinc pyrithione), commonly 1-hydroxy-2-pyridinethione salts inplatelet particle form. In an embodiment, the 1-hydroxy-2-pyridinethionesalts in platelet particle form have an average particle size of up toabout 20 microns, or up to about 5 microns, or up to about 2.5 microns.Salts formed from other cations, such as sodium, may also be suitable.Pyridinethione anti-dandruff actives are described, for example, in U.S.Pat. Nos. 2,809,971; 3,236,733; 3,753,196; 3,761,418; 4,345,080;4,323,683; 4,379,753; and 4,470,982.

In an embodiment, in addition to the anti-dandruff active selected frompolyvalent metal salts of pyrithione, the composition further comprisesone or more anti-fungal and/or anti-microbial actives. In an embodiment,the anti-microbial active is selected from the group consisting of: coaltar, sulfur, charcoal, whitfield's ointment, castellani's paint,aluminum chloride, gentian violet, octopirox (piroctone olamine),ciclopirox olamine, undecylenic acid and its metal salts, potassiumpermanganate, selenium sulfide, sodium thiosulfate, propylene glycol,oil of bitter orange, urea preparations, griseofulvin,8-hydroxyquinoline ciloquinol, thiobendazole, thiocarbamates,haloprogin, polyenes, hydroxypyridone, morpholine, benzylamine,allylamines (such as terbinafine), tea tree oil, clove leaf oil,coriander, palmarosa, berberine, thyme red, cinnamon oil, cinnamicaldehyde, citronellic acid, hinokitol, ichthyol pale, Sensiva SC-50,Elestab HP-100, azelaic acid, lyticase, iodopropynyl butylcarbamate(IPBC), isothiazalinones such as octyl isothiazalinone, and azoles, andmixtures thereof. In an embodiment, the anti-microbial is selected fromthe group consisting of: itraconazole, ketoconazole, selenium sulfide,coal tar, and mixtures thereof.

In an embodiment, the azole anti-microbials is an imidazole selectedfrom the group consisting of: benzimidazole, benzothiazole, bifonazole,butaconazole nitrate, climbazole, clotrimazole, croconazole,eberconazole, econazole, elubiol, fenticonazole, fluconazole,flutimazole, isoconazole, ketoconazole, lanoconazole, metronidazole,miconazole, neticonazole, omoconazole, oxiconazole nitrate,sertaconazole, sulconazole nitrate, tioconazole, thiazole, and mixturesthereof, or the azole anti-microbials is a triazole selected from thegroup consisting of: terconazole, itraconazole, and mixtures thereof.When present in the composition, the azole anti-microbial active isincluded in an amount of from about 0.01% to about 5%, or from about0.1% to about 3%, or from about 0.3% to about 2%, by total weight of thecomposition. In an embodiment, the azole anti-microbial active isketoconazole. In an embodiment, the sole anti-microbial active isketoconazole.

The present invention may also comprise a combination of anti-microbialactives. In an embodiment, the combination of anti-microbial active isselected from the group of combinations consisting of: octopirox andzinc pyrithione, pine tar and sulfur, salicylic acid and zincpyrithione, salicylic acid and elubiol, zinc pyrithione and elubiol,zinc pyrithione and climbasole, octopirox and climbasole, salicylic acidand octopirox, and mixtures thereof.

In an embodiment, the composition comprises an effective amount of azinc-containing layered material. In an embodiment, the compositioncomprises from about 0.001% to about 10%, or from about 0.01% to about7%, or from about 0.1% to about 5% of a zinc-containing layeredmaterial, by total weight of the composition.

Zinc-containing layered materials may be those with crystal growthprimarily occurring in two dimensions. It is conventional to describelayer structures as not only those in which all the atoms areincorporated in well-defined layers, but also those in which there areions or molecules between the layers, called gallery ions (A. F. Wells“Structural Inorganic Chemistry” Clarendon Press, 1975). Zinc-containinglayered materials (ZLMs) may have zinc incorporated in the layers and/orbe components of the gallery ions. The following classes of ZLMsrepresent relatively common examples of the general category and are notintended to be limiting as to the broader scope of materials which fitthis definition.

Many ZLMs occur naturally as minerals. In an embodiment, the ZLM isselected from the group consisting of: hydrozincite (zinc carbonatehydroxide), basic zinc carbonate, aurichalcite (zinc copper carbonatehydroxide), rosasite (copper zinc carbonate hydroxide), and mixturesthereof. Related minerals that are zinc-containing may also be includedin the composition. Natural ZLMs can also occur wherein anionic layerspecies such as clay-type minerals (e.g., phyllosilicates) containion-exchanged zinc gallery ions. All of these natural materials can alsobe obtained synthetically or formed in situ in a composition or during aproduction process.

Another common class of ZLMs, which are often, but not always,synthetic, is layered double hydroxides. In an embodiment, the ZLM is alayered double hydroxide conforming to the formula [M²⁺ _(1−x)M³⁺_(x)(OH)₂]^(x+) A^(m−) _(x/m)·nH₂O wherein some or all of the divalentions (M²⁺) are zinc ions (Crepaldi, E L, Pava, P C, Tronto, J, Valim, JB J. Colloid Interfac. Sci. 2002, 248, 429-42).

Yet another class of ZLMs can be prepared called hydroxy double salts(Morioka, H., Tagaya, H., Karasu, M, Kadokawa, J, Chiba, K Inorg. Chem.1999, 38, 4211-6). In an embodiment, the ZLM is a hydroxy double saltconforming to the formula [M²⁺ _(1−x)M²⁺ _(+x)(OH)_(3(1−y))]⁺ A^(n−)_((1=3y)/n)·nH₂O where the two metal ions (M²⁺) may be the same ordifferent. If they are the same and represented by zinc, the formulasimplifies to [Zn_(1+x)(OH)₂]^(2x+) 2 x A⁻·nH₂O. This latter formularepresents (where x=0.4) materials such as zinc hydroxychloride and zinchydroxynitrate. In an embodiment, the ZLM is zinc hydroxychloride and/orzinc hydroxynitrate. These are related to hydrozincite as well wherein adivalent anion replace the monovalent anion. These materials can also beformed in situ in a composition or in or during a production process.

In an embodiment, the composition comprises basic zinc carbonate.Commercially available sources of basic zinc carbonate include ZincCarbonate Basic (Cater Chemicals: Bensenville, Ill., USA), ZincCarbonate (Shepherd Chemicals: Norwood, Ohio, USA), Zinc Carbonate (CPSUnion Corp.: New York, N.Y., USA), Zinc Carbonate (Elementis Pigments:Durham, UK), and Zinc Carbonate AC (Bruggemann Chemical: Newtown Square,Pa., USA). Basic zinc carbonate, which also may be referred tocommercially as “Zinc Carbonate” or “Zinc Carbonate Basic” or “ZincHydroxy Carbonate”, is a synthetic version consisting of materialssimilar to naturally occurring hydrozincite. The idealized stoichiometryis represented by Zn₅(OH)₆(CO₃)₂ but the actual stoichiometric ratioscan vary slightly and other impurities may be incorporated in thecrystal lattice.

In embodiments having a zinc-containing layered material and apyrithione or polyvalent metal salt of pyrithione, the ratio ofzinc-containing layered material to pyrithione or a polyvalent metalsalt of pyrithione is from about 5:100 to about 10:1, or from about 2:10to about 5:1, or from about 1:2 to about 3:1.

Hair Care Compositions

Exemplary hair care rinse-off hair care compositions can include anaqueous carrier, which can be present at a level of from about 5% toabout 95%, or from about 60% to about 85%. The aqueous carrier maycomprise water, or a miscible mixture of water and organic solvent.Non-aqueous carrier materials can also be employed.

In an embodiment of the present invention, a surfactant may be presentin the range of about 0.1% to about 40%, in a further embodiment, fromabout 0.5% to about 30%, in a further embodiment, from about 1% to about25%.

Such rinse-off hair care compositions can include one or more detersivesurfactants. The detersive surfactant component can be included toprovide cleaning performance to the product. The detersive surfactantcomponent in turn comprises anionic detersive surfactant, zwitterionicor amphoteric detersive surfactant, or a combination thereof. Arepresentative, non-limiting, list of anionic surfactants includesanionic detersive surfactants for use in the compositions can includeammonium lauryl sulfate, ammonium laureth sulfate, triethylamine laurylsulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate,triethanolamine laureth sulfate, monoethanolamine lauryl sulfate,monoethanolamine laureth sulfate, diethanolamine lauryl sulfate,diethanolamine laureth sulfate, lauric monoglyceride sodium sulfate,sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate,potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroylsarcosinate, lauryl sarcosine, cocoyl sarcosine, ammonium cocoylsulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroylsulfate, potassium cocoyl sulfate, potassium lauryl sulfate,triethanolamine lauryl sulfate, triethanolamine lauryl sulfate,monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodiumtridecyl benzene sulfonate, sodium dodecyl benzene sulfonate, sodiumcocoyl isethionate and combinations thereof. In one example, the anionicsurfactant can be sodium lauryl sulfate or sodium laureth sulfate. Theconcentration of the anionic surfactant component in the product can besufficient to provide a desired cleaning and/or lather performance, andgenerally ranges from about 2% to about 40%.

Amphoteric detersive surfactants suitable for use in the rinse-off haircare compositions are well known in the art, and include thosesurfactants broadly described as derivatives of aliphatic secondary andtertiary amines in which an aliphatic radical can be straight orbranched chain and wherein an aliphatic substituent can contain fromabout 8 to about 18 carbon atoms such that one carbon atom can containan anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate,phosphate, or phosphonate. Examples of compounds falling within thisdefinition can be sodium 3-dodecyl-aminopropionate, sodium3-dodecylaminopropane sulfonate, sodium lauryl sarcosinate,N-alkyltaurines such as the one prepared by reacting dodecylamine withsodium isethionate according to the teaching of U.S. Pat. No. 2,658,072,N-higher alkyl aspartic acids such as those produced according to theteaching of U.S. Pat. No. 2,438,091, and products described in U.S. Pat.No. 2,528,378. Other examples of amphoteric surfactants can includesodium lauroamphoacetate, sodium cocoamphoactetate, disodiumlauroamphoacetate disodium cocodiamphoacetate, and mixtures thereof.Amphoacetates and diamphoacetates can also be used.

Zwitterionic detersive surfactants suitable for use in the rinse-offhair care compositions are well known in the art, and include thosesurfactants broadly described as derivatives of aliphatic quaternaryammonium, phosphonium, and sulfonium compounds, in which aliphaticradicals can be straight or branched chains, and wherein an aliphaticsubstituent can contain from about 8 to about 18 carbon atoms such thatone carbon atom can contain an anionic group, e.g., carboxy, sulfonate,sulfate, phosphate, or phosphonate. Other zwitterionic surfactants caninclude betaines, including cocoamidopropyl betaine.

In a further embodiment of the present invention, the hair carecomposition may comprise an cationic surfactant.

The liquid rinse off hair care composition can comprise one or morephases. Such hair care compositions can include a cleansing phase and/ora benefit phase (i.e., a single- or multi-phase composition). Each of acleansing phase or a benefit phase can include various components. Thecleansing phase and the benefit phase can be blended, separate, or acombination thereof. The cleansing phase and the benefit phase can alsobe patterned (e.g. striped).

The cleansing phase of a hair care composition can include at least onesurfactant. The cleansing phase can be an aqueous structured surfactantphase and constitute from about 5% to about 20%, by weight of the haircare composition. Such a structured surfactant phase can include sodiumtrideceth(n) sulfate, hereinafter STnS, wherein n can define averagemoles of ethoxylation. n can range, for example, from about 0 to about3; from about 0.5 to about 2.7, from about 1.1 to about 2.5, from about1.8 to about 2.2, or n can be about 2. When n can be less than 3, STnScan provide improved stability, improved compatibility of benefit agentswithin the hair care compositions, and increased mildness of thecompositions as disclosed in U.S. Pre-Grant Publication No. 2010/009285A1.

The cleansing phase can also comprise at least one of an amphotericsurfactant and a zwitterionic surfactant. Suitable amphoteric orzwitterionic surfactants (in addition to those cited herein) caninclude, for example, those described in U.S. Pat. Nos. 5,104,646 and5,106,609.

A cleansing phase can comprise a structuring system. A structuringsystem can comprise, optionally, a non-ionic emulsifier, optionally,from about 0.05% to about 5%, by weight of the hair care composition, ofan associative polymer, and an electrolyte.

The hair care composition can optionally be free of sodium laurylsulfate, hereinafter SLS, and can comprise at least a 70% lamellarstructure. However, the cleansing phase could comprise at least onesurfactant, wherein the at least one surfactant includes SLS. Suitableexamples of SLS are described in U.S. Pre-Grant Publication No.2010/0322878 A1.

Rinse-off hair care compositions can also include a benefit phase. Thebenefit phase can be hydrophobic and/or anhydrous. The benefit phase canalso be substantially free of surfactant. A benefit phase can alsoinclude a benefit agent. In particular, a benefit phase can comprisefrom about 0.1% to about 50% benefit agent by weight of the hair carecomposition. The benefit phase can alternatively comprise less benefitagent, for example, from about 0.5% to about 20% benefit agent, byweight of the hair care composition. Examples of suitable benefit agentscan include petrolatum, glyceryl monooleate, mineral oil, natural oils,and mixtures thereof. Additional examples of benefit agents can includewater insoluble or hydrophobic benefit agents. Other suitable benefitagents are described in U.S. Pre-Grant Publication No. 2012/0009285 A1.

Non-limiting examples of glycerides suitable for use as hydrophobic hairbenefit agents herein can include castor oil, safflower oil, corn oil,walnut oil, peanut oil, olive oil, cod liver oil, almond oil, avocadooil, palm oil, sesame oil, vegetable oils, sunflower seed oil, soybeanoil, vegetable oil derivatives, coconut oil and derivatized coconut oil,cottonseed oil and derivatized cottonseed oil, jojoba oil, cocoa butter,and combinations thereof.

Non-limiting examples of alkyl esters suitable for use as hydrophobichair benefit agents herein can include isopropyl esters of fatty acidsand long chain esters of long chain (i.e. C10-C24) fatty acids, e.g.,cetyl ricinoleate, non-limiting examples of which can include isopropylpalmitate, isopropyl myristate, cetyl riconoleate, and stearylriconoleate. Other example can include hexyl laurate, isohexyl laurate,myristyl myristate, isohexyl palmitate, decyl oleate, isodecyl oleate,hexadecyl stearate, decyl stearate, isopropyl isostearate, diisopropyladipate, diisohexyl adipate, dihexyldecyl adipate, diisopropyl sebacate,acyl isononanoate lauryl lactate, myristyl lactate, cetyl lactate, andcombinations thereof.

Non-limiting examples of polyglycerin fatty acid esters suitable for useas hydrophobic hair benefit agents herein can include decaglyceryldistearate, decaglyceryl diisostearate, decaglyceryl monomyriate,decaglyceryl monolaurate, hexaglyceryl monooleate, and combinationsthereof.

Rinse-Off Conditioner Composition

The conditioner composition described herein comprises a sum of total0.0001% to about 2% ofalpha,alpha,6,6-tetramethylbicyclo[3.1.1]hept-2-ene-propanal) and one ormore malodor reduction materials having a Sulfur MORV>3; b) from about0.01% to about 10% of selenium sulfide; and from about 0.1% to about 10%of a cationic surfactant or a mixture of cationic surfactants and anaqueous carrier. The conditioner composition may also comprise aconditioner gel matrix comprising part or all of the cationicsurfactant, whereas the conditioner gel network may also comprise one ormore high melting point fatty compounds (i.e. fatty alcohols), and ansecond aqueous carrier.

The conditioner gel matrix of the conditioner composition includes acationic surfactant or a cationic surfactant system. The cationicsurfactant system can be selected from: mono-long alkyl quaternizedammonium salt; a combination of mono-long alkyl quaternized ammoniumsalt and di-long alkyl quaternized ammonium salt; mono-long alkylamidoamine salt; a combination of mono-long alkyl amidoamine salt anddi-long alkyl quaternized ammonium salt, a combination of mono-longalkyl amindoamine salt and mono-long alkyl quaternized ammonium salt.The cationic surfactant system can be included in the composition at alevel by weight of from about 0.1% to about 10%, from about 0.5% toabout 8%, from about 0.8% to about 5%, and from about 1.0% to about 4%.

The conditioner gel matrix of the conditioner composition includes oneor more high melting point fatty compounds. Suitable fatty alcoholsinclude, for example, cetyl alcohol, stearyl alcohol, behenyl alcohol,and mixtures thereof. The high melting point fatty compound can beincluded in the conditioner composition at a level of from about 0.1% toabout 20%, alternatively from about 1% to about 15%, and alternativelyfrom about 1.5% to about 8% by weight of the composition. Theconditioner gel matrix of the conditioner composition includes a secondaqueous carrier. The second aqueous carrier may comprise water, or amiscible mixture of water and organic solvent.

Leave-on Treatment Composition

The leave-on treatment composition described herein comprises a sum oftotal 0.0001% to about 2% ofalpha,alpha,6,6-tetramethylbicyclo[3.1.1]hept-2-ene-propanal) and one ormore malodor reduction materials having a Sulfur MORV>3; b) from about0.01% to about 10% of selenium sulfide; and from about 0.1% to about 10%of a cationic surfactant or a mixture of cationic surfactants and anaqueous carrier. The leave-on treatment may also comprise one or morerheology modifiers and a third aqueous carrier.

In one embodiment the leave-on treatment may include a conditioner gelmatrix as described above (in the rinse-off conditioner description).

In another embodiment the leave-on treatment may include one or morerheology modifiers. Any suitable rheology modifier can be used. In anembodiment, the leave-on treatment may comprise from about 0.01% toabout 3% of a rheology modifier, alternatively from about 0.1% to about1% of a rheology modifier,

Additional Components

The conditioner compositions, and/or leave-on treatments describedherein may optionally comprise one or more additional components knownfor use in hair care or personal care products,

Non-limiting examples of additional components for use in the hair carecompositions include conditioning agents (silicone or non-siliconeconditioning agents), natural cationic deposition polymers, syntheticcationic deposition polymers, anti-dandruff agents, particles,suspending agents, paraffinic hydrocarbons, propellants, viscositymodifiers, dyes, non-volatile solvents or diluents (water-soluble andwater-insoluble), pearlescent aids, foam boosters, additionalsurfactants or nonionic cosurfactants, pediculocides, pH adjustingagents, perfumes, preservatives, proteins, skin active agents,sunscreens, UV absorbers, and vitamins.

The rinse-off hair care composition can be applied by a variety ofmeans, including by rubbing, wiping or dabbing with hands or fingers, orby means of an implement and/or delivery enhancement device.Non-limiting examples of implements include a sponge or sponge-tippedapplicator, a mesh shower puff, a swab, a brush, a wipe (e.g., washcloth), a loofah, and combinations thereof. Non-limiting examples ofdelivery enhancement devices include mechanical, electrical, ultrasonicand/or other energy devices. Employment of an implement or device canhelp delivery of the particulate antimicrobial agent to target regions,such as, for example, hair follicles and undulations that can exist inthe underarm. The rinse-off care product can be sold together with suchan implement or device. Alternatively, an implement or device can besold separately but contain indicium to indicate usage with a rinse-offcare product. Implements and delivery devices can employ replaceableportions (e.g., the skin interaction portions), which can be soldseparately or sold together with the rinse-off care product in a kit.

Test Methods

Malodor reduction materials may be separated from mixtures, includingbut not limited to finished products such as consumer products andidentified, by analytical methods that include GC-MS and/or NMR.

Test Method for Determining Saturation Vapour Pressure (VP)

The saturation Vapour Pressure (VP) values are computed for each PRM inthe perfume mixture being tested. The VP of an individual PRM iscalculated using the VP Computational Model, version 14.02 (Linux)available from Advanced Chemistry Development Inc. (ACD/Labs) (Toronto,Canada) to provide the VP value at 25° C. expressed in units of torr.The ACD/Labs' Vapor Pressure model is part of the ACD/Labs model suite.

Test Method for Determining the Logarithm of the Octanol/Water PartitionCoefficient (log P)

The value of the log of the Octanol/Water Partition Coefficient (log P)is computed for each PRM in the perfume mixture being tested. The log Pof an individual PRM is calculated using the Consensus log PComputational Model, version 14.02 (Linux) available from AdvancedChemistry Development Inc. (ACD/Labs) (Toronto, Canada) to provide theunitless log P value. The ACD/Labs' Consensus log P Computational Modelis part of the ACD/Labs model suite.

Test Method for the Generation of Molecular Descriptors

In order to conduct the calculations involved in the computed-value testmethods described herein, the starting information required includes theidentity, weight percent, and molar percent of each PRM in the perfumebeing tested, as a proportion of that perfume, wherein all PRMs in theperfume composition are included in the calculations. Additionally foreach of those PRMs, the molecular structure, and the values of variouscomputationally-derived molecular descriptors are also required, asdetermined in accordance with the Test Method for the Generation ofMolecular Descriptors described herein.

For each PRM in a perfume mixture or composition, its molecularstructure is used to compute various molecular descriptors. Themolecular structure is determined by the graphic molecular structurerepresentations provided by the Chemical Abstract Service (“CAS”), adivision of the American Chemical Society, Columbus, Ohio, U.S.A. Thesemolecular structures may be obtained from the CAS Chemical RegistrySystem database by looking up the index name or CAS number of each PRM.For PRMs, which at the time of their testing are not yet listed in theCAS Chemical Registry System database, other databases or informationsources may be used to determine their structures. For a PRM which haspotentially more than one isomer present, the molecular descriptorcomputations are conducted using the molecular structure of only one ofthe isomers, which is selected to represent that PRM. The selection ofisomer is determined by the relative amount of extension in themolecular structures of the isomers. Of all the isomers of a given PRM,it is the isomer whose molecular structure that is the most prevalentwhich is the one that is selected to represent that PRM. The structuresfor other potential isomers of that PRM are excluded from thecomputations. The molecular structure of the isomer that is the mostprevalent is paired with the concentration of that PRM, where theconcentration reflects the presence of all the isomers of that PRM thatare present.

A molecule editor or molecular sketching software program, such asChemDraw (CambridgeSoft/PerkinElmer Inc., Waltham, Mass., U.S.A.), isused to duplicate the 2-dimensional molecular structure representingeach PRM. Molecular structures should be represented as neutral species(quaternary nitrogen atoms are allowed) with no disconnected fragments(e.g., single structures with no counter ions). The winMolconn programdescribed below can convert any deprotonated functional groups to theneutral form by adding the appropriate number of hydrogen atoms and willdiscard the counter ion.

For each PRM, the molecular sketching software is used to generate afile which describes the molecular structure of the PRM. The file(s)describing the molecular structures of the PRMs is subsequentlysubmitted to the computer software program winMolconn, version 1.0.1.3(Hall Associates Consulting, Quincy, Mass., U.S.A., www.molconn.com), inorder to derive various molecular descriptors for each PRM. As such, itis the winMolconn software program which dictates the structurenotations and file formats that are acceptable options. These optionsinclude either a MACCS SDF formatted file (i.e., a Structure-Data File);or a Simplified Molecular Input Line Entry Specification (i.e., a SMILESstring structure line notation) which is commonly used within a simpletext file, often with a “.smi” or “.txt” file name extension. The SDFfile represents each molecular structure in the format of a multi-linerecord, while the syntax for a SMILES structure is a single line of textwith no white space. A structure name or identifier can be added to theSMILES string by including it on the same line following the SMILESstring and separated by a space, e.g.: C1=CC=CC=C1 benzene.

The winMolconn software program is used to generate numerous moleculardescriptors for each PRM, which are then output in a table format.Specific molecular descriptors derived by winMolconn are subsequentlyused as inputs (i.e., as variable terms in mathematical equations) for avariety of computer model test methods in order to calculate values suchas: saturation Vapour Pressure (VP); Boiling Point (BP); logarithm ofthe Octanol/Water Partition Coefficient (log P); Odour DetectionThreshold (ODT); Malodour Reduction Value (MORV); and/or UniversalMalodour Reduction Value (Universal MORV) for each PRM. The moleculardescriptor labels used in the models' test method computations are thesame labels reported by the winMolconn program, and their descriptionsand definitions can be found listed in the winMolconn documentation. Thefollowing is a generic description of how to execute the winMolconnsoftware program and generate the required molecular structuredescriptors for each PRM in a composition.

Computing Molecular Structure Descriptors using winMolconn:

-   -   1) Assemble the molecular structure for one or more perfume        ingredients in the form of a MACCS Structure-Data File, also        called an SDF file, or as a SMILES file.    -   2) Using version 1.0.1.3 of the winMolconn program, running on        an appropriate computer, compute the full complement of        molecular descriptors that are available from the program, using        the SDF or SMILES file described above as input.        -   a. The output of winMolconn is in the form of an ASCII text            file, typically space delimited, containing the structure            identifiers in the first column and respective molecular            descriptors in the remaining columns for each structure in            the input file.    -   3) Parse the text file into columns using a spreadsheet software        program or some other appropriate technique. The molecular        descriptor labels are found on the first row of the resulting        table.    -   4) Find and extract the descriptor columns, identified by the        molecular descriptor label, corresponding to the inputs required        for each model.        -   a. Note that the winMolconn molecular descriptor labels are            case-sensitive.            MORV Calculation            1.) Input Molecular Descriptor values as determined via the            method above into the following equation:            MORV=−0.0035+0.8028×(SHCsatu)+2.1673×(xvp7)−1.3507×(c1C1C3d)+0.61496×(c1C1O2)+0.00403×(idc)−0.23286×(nd2).            This equation relates a material's effectiveness in reducing            the malodor 3-mercapto-3-methylhexan-1-ol (thiol based            malodors)            2.) For purpose of the present application, a material's            MORV is the highest MORV value from the above equation.            The purpose of this experimental design is to determine            whether malodor reducing compositions show benefit in            reducing the perception of malodor from selenium            sulfide-containing shampoos.            Procedure:

Six malodor reduction accords are dosed into unperfumed selenium sulfideshampoo at 4 different levels; samples are allowed to equilibrate atroom temperature for at least 1 week before evaluating.

#1 Malodor Reduction Composition (MRC)

CAS MATERIAL Wt % 13877-91-3 (3Z)-3,7-dimethylocta-1,3,6- 3.000 triene5413-60-5 (3a,4,5,6,7,7a-hexahydro-1H- 10.000 4,7-methanoinden-6-ylacetate t 33885-52-8 alpha,alpha,6,6-tetramethyl 1.500bicyclo[3.1.1]hept-2-ene- propanal) 23787-90-81,3,4,6,7,8alpha-hexahydro- 14.000 1,1,5,5-tetramethyl-2H-2,4alpha-methanophtalen- 8(5H)-one 4430-31-3 3,4,4a,5,6,7,8,8a- 10.000octahydrochromen-2-one 300371-33-9 2,3-dihydro-1,1-1H-dimethyl- 1.500indene-ar-propanal 55066-48-3 3-methyl-5-phenylpentan-1-ol 10.000139504-68-0 1-((2-(tert- 10.000 butyl)cyclohexyl)oxy)butan-2- ol3681-73-0 (E)-3,7-dimethylocta-2,6-dien- 40.000 1-yl palmitate)

#2 Malodor Reduction Composition (MRC)

CAS MATERIAL Wt % 58430-94-7 3,5,5-trimethylhexyl acetate 56 33885-52-8alpha,alpha,6,6-tetramethyl 18 bicyclo[3.1.1]hept-2-ene- propanal)1139-30-6 4,5-epoxy-4,11,11-trimethyl-8- 0.5methylenebicyclo(7.2.0)undecane) 27606-09-3 2,4-dimethyl-4,4a,5,9b- 15tetrahydroindeno[1,2- d][1,3]dioxine 127-42-4(E)-1-(2,6,6-trimethyl-1-cyclohex- 2 2-enyl)pent-1-en-3-one 23787-90-8(1,3,4,6,7,8alpha-hexahydro- 5 1,1,5,5-tetramethyl-2H-2,4alpha-methanophtalen-8(5H)-one 68912-13-0 8,8-dimethyl-3a,4,5,6,7,7a- 3.5hexahydro-1H-4,7-methanoinden- 6-yl propionate

#3 Malodor Reduction Composition (MRC)

CAS MATERIAL Wt % 5413-60-5 (3a,4,5,6,7,7a-hexahydro- 15.0001H-4,7-methanoinden-6-yl acetate 23787-90-8 1,3,4,6,7,8alpha-hexahydro-5.000 1,1,5,5-tetramethyl-2H- 2,4alpha-methanophtalen- 8(5H)-one300371-33-9 2,3-dihydro-1,1-1H- 1.000 dimethyl-indene-ar-propanal55066-48-3 3-methyl-5-phenylpentan-1- 49.000 ol 139504-68-0 1-((2-(tert-10.000 butyl)cyclohexyl)oxy)butan- 2-ol 3681-73-0(E)-3,7-dimethylocta-2,6- 20.000 dien-1-yl palmitate)

#4 Malodor Reduction Composition (MRC)

CAS MATERIAL Wt % 23787-90-8 1,3,4,6,7,8alpha-hexahydro- 40.0001,1,5,5-tetramethyl-2H- 2,4alpha-methanophtalen- 8(5H)-one 300371-33-92,3-dihydro-1,1-1H- 10.000 dimethyl-indene-ar-propanal 55066-48-33-methyl-5-phenylpentan-1- 10.000 ol 3681-73-0 (E)-3,7-dimethylocta-2,6-40.000 dien-1-yl palmitate)

#5 Malodor Reduction Composition (MRC)

CAS MATERIAL Wt % 58430-94-7 3,5,5-trimethylhexyl acetate 2.05 98-52-24-tert-butyl cyclohexane 0.25 32210-23-4 4-(tert-butyl)cyclohexyl 7.6acetate 30772-79-3 Octahydro-1H-4,7- 0.28 methanoindene-1- carbaldehyde63500-71-0 2-isobutyl-4-hydroxy-4- 9.5 methyltetrahydropyran 1 101-84-8DIPHENYL OXIDE 0.28 19870-74-7 Cedryl Methyl Ether 62.2 23787-90-8(1,3,4,6,7,8alpha-hexahydro- 9.5 1,1,5,5-tetramethyl-2H-2,4alpha-methanophtalen- 8(5H)-one 93-16-3 (Z)-1,2-dimethoxy-4-(prop-4.46 1-en-1-yl)benzene 55066-48-3 3-methyl-5-phenylpentan-1- 3.8 ol24851-98-7 methyl 2-(3-oxo-2- 0.08 pentylcyclopentyl)acetate

#6 Malodor Reduction Composition (MRC)

CAS MATERIAL Wt % 58430-94-7 3,5,5-trimethylhexyl acetate 40 5413-60-5(3a,4,5,6,7,7a-hexahydro-1H- 20 4,7-methanoinden-6-yl acetate t23787-90-8 1,3,4,6,7,8alpha-hexahydro- 20 1,1,5,5-tetramethyl-2H-2,4alpha-methanophtalen- 8(5H)-one 300371-33-92,3-dihydro-1,1-1H-dimethyl- 10 indene-ar-propanal 55066-48-33-methyl-5-phenylpentan-1-ol 10

Samples to a depth of ˜1 cm are placed into plastic cups; cups arecovered with lids, then lids are removed for evaluation. Each sample isevaluated by 4 trained odor panelists for the presence of sulfurmalodor. The unperfumed shampoo with no Malodor Reduction Composition(MRC) is set as positive control (ie, “2”) while a separate batch of thesame shampoo formula, sans selenium sulfide, is set as negative control(ie, “0”). Additionally, a 50:50 blend of the 2 unperfumed shampoos(with and without selenium sulfide) is created and this is set as anadditional “low sulfur” benchmark for improved coverage (Ie, “1”).Sample presentation is randomized.

Instructions are provided to the panelists as follows:

-   -   1) Please smell sample labeled “Control”. Note the amount of        sulfur base odor. This is your benchmark for subsequent        evaluations. You can also refer to “Low Sulfur Control” and “No        Sulfur Control” as needed, however, the scale is relative to        “Control”.    -   2) Please evaluate each sample by removing the lid, and indicate        the amount of sulfur relative to the control that you can detect        in each sample. You may or may not be able to smell perfume        materials in the test samples; please assess only for amount of        sulfur odor using the scale below:        -   0=I cannot smell any sulfur odor at all (you can refer to            “No Sulfur Control”)        -   1=I smell some sulfur odor, but less than the “control” (You            can refer to “Low Sulfur Control)        -   2=I smell sulfur odor equal to the control        -   3=I smell more sulfur odor than in the control            Panelists evaluate each level series as a set, taking a            break in between sets to avoid olfactive saturation.            Results

Round 1-0.01% Malodor

Reduction Composition (MRC)

Panelist Panelist Panelist Panelist 1 2 3 4 Avg MRC 1 1 0 1 0.5 0.625MRC 2 1 0 0 0.5 0.375 MRC 3 1 1 2 1 1.25 MRC 4 1 2 1 2 1.5 MRC 5 2 1.5 12 1.625 MRC 6 1 1 1 1 1

Round 2-0.05% Malodor

Reduction composition (MRC) MRC 1 0 1 2 0 0.75 MRC 2 0 1 0.5 0 0.375 MRC3 1 1.5 1 1 1.125 MRC 4 0 2 1 1 1 MRC 5 0 2 2 2 1.5 MRC 6 0 2 2 1 1.25

Round 3-0.1% Malodor

Reduction composition (MRC) MRC 1 1 0 1 1 0.75 MRC 2 0 0 0 0 0 MRC 3 1 00 1 0.5 MRC 4 0 1 1 1 0.75 MRC 5 1 0.5 2 2 1.375 MRC 6 0 1 2 1 1

Round 4-0.15% Malodor

Reduction composition (MRC) MRC 1 1 0 1.5 1 0.875 MRC 2 0 1 0.5 0 0.375MRC 3 0 1 2 1 1 MRC 4 0 1 1 1 0.75 MRC 5 0 2 2 1 1.25 MRC 6 1 1 1 1 1SummaryMRC 1, MRC 2, MRC 3 and MRC 4 all show considerable reduction (<1 Avg)in perceived sulfur levels at one or more levels tested. Additionally,MRC 2 showed reduction at all levels tested, with all panelistsassigning a zero or “no sulfur” rating at the 0.1% added level.As a follow up, the MRC 2 is diluted in 100 deg F. tap water at a ratioof 1 ml shampoo to 75 ml water; these samples are placed into cups,capped, and agitated until the shampoo is dissolved. They areimmediately evaluated by 2 panelists to determine if sulfur odor ispresent in the dilute samples.

Panelist 1 Panelist 4 MRC 2 @ 0.01%, diluted 1:75 in 1 1.5 warm water(100 F.) MRC 2 @ 0.05%, diluted 1:75 in 0.5 0.5 warm water (100 F.) MRC2 @ 0.10%, diluted 1:75 in 0 0 warm water (100 F.) MRC 2 @ 0.15%,diluted 1:75 in 0 0 warm water (100 F.)In dilution, the perceived benefit holds, particularly at the 0.1% and0.15% levels.ConclusionMalodor Reduction Composition's demonstrates effectiveness in themasking/blocking of selenium sulfide odor. In the present invention,this understanding can be leveraged in formulation strategies forselenium sulfide containing hair care compositions.I. Hair Switch Selection and Preparation—for Ah Tests

-   -   a) For each product, a 20 gram hair switch is used, cleaned and        stripped of perfume. Cleaning may be done via external vendor        (ie, ATL 2× baking soda/main mix) or internally via local        documented procedures. (New hair switches can be pre-washed with        unperfumed shampoo before very first use)    -   b) Each hair switch is evaluated before each use to ensure no        contamination/off odors.        II. Shampoo Fragrance Profile    -   a) A neat product is evaluated; and a neat sulfur score is        recorded    -   b) The water temperature may be adjusted to 100 F/38 C and 1.5        gal/5.7 l per min; and hair is wetted for 20 seconds.    -   c) 2 ml product is applied; and lather is produced for 30        seconds.    -   d) Odor is evaluated using sulfur scoring and comments are        recorded.

TABLE 4 Evaluate MRC2 On Switch vs Negative Control In-Use Evaluation 20gram hair switch used, 2 ml product; 100 F. water according to themethod described above. Sulfur Odor Neat Lather Sulfur Lather ProductScale (0-3) Comments Scale (0-3) Comments Selenium Sulfide 2 sulfur 2sulfur Unperfumed Shampoo odor odor Non Malodor Reducing Accord¹ 1sulfur odor + 1 sulfur odor + @ 0.1% in Selenium Sulfide rose powderyrose powdery Shampoo note note MRC2 @ 0.1% in Selenium 0 ozonic, 0ozonic. Sulfide Shampoo floral Floral 1. Non-Malodor Reducing AccordMaterial % CAS Citronellol 20 106-22-920 Linalool 30 78-70-6 PhenylEthyl Alcohol 50 60-12-8 Sulfur Odor Scale: 0 = I cannot smell anysulfur odor at all (you can refer to “No Sulfur Control”) 1 = I smellsome sulfur odor, but less than the “control” (You can refer to “LowSulfur Control”) 2 = I smell sulfur odor equal to the control 3 = Ismell more sulfur odor than in the control

TABLE 5 Evaluate MRC 2 On Switch vs non malodor reducing accord-0.01%Levels In-Use Evaluation 20 gram hair switch used, 2 ml product; 100 F.water according to the method described above. Neat Sulfur Odor NeatLather Sulfur Lather Product Scale (0-3) Comments Scale (0-3) CommentsSelenium Sulfide 2 sulfur 2 sulfur Unperfumed Shampoo odor odor Non-malodor reducing 1.5 slight rosy, 2 sulfur accord¹@ 0.01% in Seleniumnoticeable odor Sulfide Shampoo (ref batch sulfur MBRC 2 @ 0.01% in 0.5slight ozonic, 0.5 Slight ozonic, Selenium Sulfide Shampoo very slightvery slight sulfur sulfur 1. Non-Malodor Reducing Accord Material % CASCitronellol 20 106-22-920 Linalool 30 78-70-6 Phenyl Ethyl Alcohol 5060-12-8 Sulfur Odor Scale: 0 = I cannot smell any sulfur odor at all(you can refer to “No Sulfur Control”) 1 = I smell some sulfur odor, butless than the “control” (You can refer to “Low Sulfur Control”) 2 = Ismell sulfur odor equal to the control 3 = I smell more sulfur odor thanin the controlConclusion

This series of experiments indicates that malodor reducing ingredientsor a combination of those, such as MRC2, provides a malodor blockingbenefit both in neat product and during the lather phase. This benefitgoes beyond the masking benefit that would be provided by a non-malodorreducing perfume. In table 4 (0.1% data), the non-malodor reducingaccord exhibits malodor interference via masking benefit due to theperfume intensity imparted by the ingredients. In table 5 (the 0.01%data) it is demonstrated that as level is reduced the masking benefit ofthe non-malodor-reducing accord is decreased, while the malodor blockingproperty of the MRC2 is maintained.

Examples Shampoo with Malodor Reducing Composition

An example of Shampoo compositions prepared with malodor reductioncomposition, according to the compositions shown in Example 1.

1 2 3 Ingredient Wt % Ammonium Laureth Sulfate¹ 14.1 14.1 14.1 AmmoniumLauryl Sulfate ² 3.1 3.1 3.1 Ammonium Xylenesulfonate³ 0.45 0.45 0.45TWEEN 60⁴ 3.0 3.0 3.0 Polyquaternium-10⁵ 0.35 0.35 0.35 CetrimoniumChloride⁶ 0.5 0.5 0.5 Selenium Sulfide⁷ 1.0 1.0 1.0 Dimethicone⁸ 0.600.60 0.60 Ethylene Glycol Distearate⁹ 3.0 3.0 3.0 Cocamide MEA¹⁰ 3.0 3.03.0 Zinc Pyrithione¹¹ — 0.2 0.2 Zinc Carbonate¹² — — 1.61 Neat Fragrance1.1 0.75 0.75 Malodor reducing composition 0.25 0.25 0.175 CetylAlcohol¹³ 0.42 0.42 0.42 DMDM Hydantoin 0.40 0.40 0.40 Sodium Chloride0.30 0.30 0.30 Stearyl Alcohol¹⁴ 0.20 0.20 0.20 HydroxypropylMethylcellulose¹⁵ 0.02 0.02 0.02 Water Q.S. Q.S. Q.S. ¹Ammonium LaurethSulfate at 25% active, supplier: P&G ² Ammonium Lauryl Sulfate at 25%active, supplier: P&G ³Ammonium Xylene Sulfonate 40% active, supplier:Stepan ⁴Polysorbate 60, upplier: Croda ⁵UCARE Polymer LR400, supplier-Dow Chemical ⁶cetrimonium chloride, supplier - Croda ⁷Seleniumdisulfide, supplier Eskay ⁸Viscasil 330M from Momentive PerformanceMaterials with a viscosity of 330,000 cSt (centistokes). ⁹EthyleneGlycol Disterate, supplier: Stepan ¹⁰Ninol COMF from the Stepan Company¹¹Zinc Pyrithione, supplier Lonza ¹²Zinc Carbonate Basic, supplier PanContinental Chemical ¹³Cetyl Alcohol, supplier P&G ¹⁴Stearyl Alcohol,supplier P&G ¹⁵Methocel, supplier Dow Chemical

4 5 6 Ingredient Wt % Ammonium Laureth Sulfate¹ 14.1 14.1 14.1 AmmoniumLauryl Sulfate ² 3.1 3.1 3.1 Ammonium Xylenesulfonate³ 0.45 0.45 0.45TWEEN 60⁴ 3.0 3.0 3.0 Polyquaternium-10⁵ 0.35 0.35 0.35 CetrimoniumChloride⁶ 0.5 0.5 0.5 Selenium Sulfide⁷ 1.0 0.2 0.2 Dimethicone⁸ 0.600.60 0.60 Ethylene Glycol Distearate⁹ 3.0 3.0 3.0 Cocamide MEA¹⁰ 3.0 3.03.0 Zinc Pyrithione¹¹ — 1.0 1.0 Zinc Carbonate¹² — — 1.61 Neat Fragrance0.65 0.85 1.0 Malodor reducing composition 0.175 0.175 0.175 CetylAlcohol¹³ 0.42 0.42 0.42 DMDM Hydantoin 0.40 0.40 0.40 Sodium Chloride0.30 0.30 0.30 Stearyl Alcohol¹⁴ 0.20 0.20 0.20 HydroxypropylMethylcellulose¹⁵ 0.02 0.02 0.02 Water Q.S. Q.S. Q.S. ¹Ammonium LaurethSulfate at 25% active, supplier: P&G ² Ammonium Lauryl Sulfate at 25%active, supplier: P&G ³Ammonium Xylene Sulfonate 40% active, supplier:Stepan ⁴Polysorbate 60, upplier: Croda ⁵UCARE Polymer LR400, supplier-Dow Chemical ⁶cetrimonium chloride, supplier - Croda ⁷Seleniumdisulfide, supplier Eskay ⁸Viscasil 330M from Momentive PerformanceMaterials with a viscosity of 330,000 cSt (centistokes). ⁹EthyleneGlycol Disterate, supplier: Stepan ¹⁰Ninol COMF from the Stepan Company¹¹Zinc Pyrithione, supplier Lonza ¹²Zinc Carbonate Basic, supplier PanContinental Chemical ¹³Cetyl Alcohol, supplier P&G ¹⁴Stearyl Alcohol,supplier P&G ¹⁵Methocel, supplier Dow Chemical

In an embodiment of the present invention, the example of Shampoocompositions (Example 5) may also be prepared with the malodor reductioncomposition according to the compositions shown in Example 2 and/orExample 3.

7 8 9 Ingredient Wt % Ammonium Laureth Sulfate¹ 14.1 14.1 14.1 AmmoniumLauryl Sulfate ² 3.1 3.1 3.1 Ammonium Xylenesulfonate³ 0.45 0.45 0.45TWEEN 60⁴ 3.0 3.0 3.0 Polyquaternium-10⁵ 0.35 0.35 0.35 CetrimoniumChloride⁶ 0.5 0.5 0.5 Sulfur⁷ 2.0 5.0 3.5 Dimethicone⁸ 0.60 0.60 0.60Ethylene Glycol Distearate⁹ 3.0 3.0 3.0 Cocamide MEA¹⁰ 3.0 3.0 3.0Selenium Sulfide ¹¹ — — — Neat Fragrance 0.85 1.1 0.95 Malodor reducingcomposition 0.175 0.25 0.25 Cetyl Alcohol¹² 0.42 0.42 0.42 DMDMHydantoin 0.40 0.40 0.40 Sodium Chloride 0.30 0.30 0.30 StearylAlcohol¹³ 0.20 0.20 0.20 Hydroxypropyl Methylcellulose¹⁴ 0.02 0.02 0.02Water Q.S. Q.S. Q.S. ¹Ammonium Laureth Sulfate at 25% active, supplier:P&G ² Ammonium Lauryl Sulfate at 25% active, supplier: P&G ³AmmoniumXylene Sulfonate 40% active, supplier: Stepan ⁴Polysorbate 60, upplier:Croda ⁵UCARE Polymer LR400, supplier- Dow Chemical ⁶cetrimoniumchloride, supplier - Croda ⁷Sulfur USP, supplier UniversalPreserv-A-Chem ⁸Viscasil 330M from Momentive Performance Materials witha viscosity of 330,000 cSt (centistokes). ⁹Ethylene Glycol Disterate,supplier: Stepan ¹⁰Ninol COMF from the Stepan Company ¹¹ ZincPyrithione, supplier Lonza ¹²Selenium disulfide, supplier Eskay ¹²CetylAlcohol, supplier P&G 13Stearyl Alcohol, supplier P&G ¹⁴Methocel,supplier Dow Chemical

10 11 12 Ingredient Wt % Ammonium Laureth Sulfate¹ 14.1 14.1 14.1Ammonium Lauryl Sulfate ² 3.1 3.1 3.1 Ammonium Xylenesulfonate³ 0.450.45 0.45 TWEEN 60⁴ 3.0 3.0 3.0 Polyquaternium-10⁵ 0.35 0.35 0.35Cetrimonium Chloride⁶ 0.5 0.5 0.5 Sulfur⁷ 2.0 2.0 2.0 Dimethicone⁸ 0.600.60 0.60 Ethylene Glycol Distearate⁹ 3.0 3.0 3.0 Cocamide MEA¹⁰ 3.0 3.03.0 Selenium Sulfide ¹¹ 0.5 0.25 0.1 Neat Fragrance 0.65 0.85 1.0Malodor reducing composition 0.175 0.175 0.175 Cetyl Alcohol¹² 0.42 0.420.42 DMDM Hydantoin 0.40 0.40 0.40 Sodium Chloride 0.30 0.30 0.30Stearyl Alcohol¹³ 0.20 0.20 0.20 Hydroxypropyl Methylcellulose¹⁴ 0.020.02 0.02 Water Q.S. Q.S. Q.S. ¹Ammonium Laureth Sulfate at 25% active,supplier: P&G ² Ammonium Lauryl Sulfate at 25% active, supplier: P&G³Ammonium Xylene Sulfonate 40% active, supplier: Stepan ⁴Polysorbate 60,upplier: Croda ⁵UCARE Polymer LR400, supplier- Dow Chemical ⁶cetrimoniumchloride, supplier - Croda ⁷Sulfur USP, supplier UniversalPreserv-A-Chem ⁸Viscasil 330M from Momentive Performance Materials witha viscosity of 330,000 cSt (centistokes). ⁹Ethylene Glycol Disterate,supplier: Stepan ¹⁰Ninol COMF from the Stepan Company ¹¹ ZincPyrithione, supplier Lonza ¹²Selenium disulfide, supplier Eskay ¹²CetylAlcohol, supplier P&G ¹³Stearyl Alcohol, supplier P&G ¹⁴Methocel,supplier Dow Chemical

13 14 15 Ingredients Wt % Sodium Laureth Sulfate¹ 14.1 11.5 11.5 SodiumLauryl Sulfate ² 3.1 1.5 1.5 Sodium Xylenesulfonate³ 0.50 3.0 3.0Cocamidopropyl Betaine⁴ — 1.3 1.3 Guar Hyrdroxypropyltrimonium chloride⁵— 0.3 0.3 PQ-76⁶ — 0.03 — Acrylamide/trimethylammoniopro- — — 0.01pylmethacrylamide⁷ Selenium Sulfide⁸ 1.0 1.0 0.2 Sulfur⁹ — — —Dimethicone¹⁰ 0.60 0.8 2.7 Ethylene Glycol Distearate¹¹ 3.0 1.5 1.5Cocamide MEA¹² 3.0 2.0 2.0 Zinc Pyrithione¹³ — — 1.0 Zinc Carbonate¹⁴ —— 1.61 Fragrance 0.65 0.85 1.0 Malodor reducing composition 0.15 0.1750.1 Cetyl Alcohol¹⁵ 0.42 0.04 0.04 Stearyl Alcohol¹⁶ 0.20 0.08 0.08 DMDMHydantoin 0.40 — — Methylchloroisothiazolinone and 0.5 0.005 0.005Methylisothiazolinone Sodium Chloride 0.30 — — HydroxypropylMethylcellulose¹⁷ 0.02 0.02 0.02 Water Q.S. Q.S. Q.S. ¹Sodium LaurethSulfate at 28% active, supplier: P&G ² Sodium Lauryl Sulfate at 29%active, supplier: P&G ³Sodium Xylene Sulfonate 40% active, supplier:Stepan ⁴Amphosol HCA from the Stepan Company ⁵Jaguar C500 from Rhodia;mw 500,000 cd 0.8 meq/g ⁶PQ-76 from Rhodia; mw 100,000 cd 1.6 meq/g⁷AM/APTAC mw 1,100,000 cd 1.8 meq/g, supplier ASI Specialty Ingredients⁸Selenium disulfide, supplier Eskay ⁹Sulfur USP, supplier UniversalPreserv-A-Chem ¹⁰Viscasil 330M from Momentive Performance Materials witha viscosity of 330,000 cSt (centistokes). ¹¹Ethylene Glycol Disterate,supplier: Stepan ¹²Ninol COMF from the Stepan Company ¹³Zinc Pyrithione,supplier Lonza ¹⁴Zinc Carbonate Basic, supplier Pan Continental Chemical¹⁵Cetyl Alcohol, supplier P&G ¹⁶Stearyl Alcohol, supplier P&G¹⁷Methocel, supplier Dow Chemical

16 17 18 Ingredients Wt % Sodium Laureth Sulfate¹ 11.5 11.5 11.5 SodiumLauryl Sulfate ² 1.5 1.5 1.5 Sodium Xylenesulfonate³ 3.0 3.0 3.0Cocamidopropyl Betaine⁴ 1.3 1.3 1.3 Guar Hyrdroxypropyltrimoniumchloride⁵ 0.3 0.3 0.3 PQ-76⁶ 0.03 0.03 — Acrylamide/trimethylammoniopro-— — 0.01 pylmethacrylamide⁷ Selenium Sulfide⁸ 1.0 — 0.1 Sulfur⁹ 2.0 5.02.0 Dimethicone¹⁰ 0.8 0.8 2.7 Ethylene Glycol Distearate¹¹ 1.5 1.5 1.5Cocamide MEA¹² 2.0 2.0 2.0 Zinc Pyrithione¹³ — — — Zinc Carbonate¹⁴ — —— Fragrance 0.85 0.85 1.0 Malodor reducing composition 0.175 0.175 0.1Cetyl Alcohol¹⁵ 0.04 0.04 0.04 Stearyl Alcohol¹⁶ 0.08 0.08 0.08 DMDMHydantoin — — — Methylchloroisothiazolinone and 0.005 0.005 0.005Methylisothiazolinone Sodium Chloride — — — HydroxypropylMethylcellulose¹⁷ 0.02 0.02 0.02 Water Q.S. Q.S. Q.S. ¹Sodium LaurethSulfate at 28% active, supplier: P&G ² Sodium Lauryl Sulfate at 29%active, supplier: P&G ³Sodium Xylene Sulfonate 40% active, supplier:Stepan ⁴Amphosol HCA from the Stepan Company ⁵Jaguar C500 from Rhodia;mw 500,000 cd 0.8 meq/g ⁶PQ-76 from Rhodia; mw 100,000 cd 1.6 meq/g⁷AM/APTAC mw 1,100,000 cd 1.8 meq/g, supplier ASI Specialty Ingredients⁸Selenium disulfide, supplier Eskay ⁹Sulfur USP, supplier UniversalPreserv-A-Chem ¹⁰Viscasil 330M from Momentive Performance Materials witha viscosity of 330,000 cSt (centistokes). ¹¹Ethylene Glycol Disterate,supplier: Stepan ¹²Ninol COMF from the Stepan Company ¹³Zinc Pyrithione,supplier Lonza ¹⁴Zinc Carbonate Basic, supplier Pan Continental Chemical¹⁵Cetyl Alcohol, supplier P&G ¹⁶Stearyl Alcohol, supplier P&G¹⁷Methocel, supplier Dow Chemical

Rinse Out Conditioner Examples

The following examples further describe and demonstrate embodimentswithin the scope of the present invention. The examples are given solelyfor the purpose of illustration and are not to be construed aslimitations of the present invention, as many variations thereof arepossible without departing from the spirit and scope of the invention.Where applicable, ingredients are identified by chemical or CTFA name,or otherwise defined below.

Components Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Polyquaternium-6 *1 0.075 — — —— Polyquaternium-6 *2 — 0.075 0.075 0.075 0.075 Zinc pyrithione *3 0.50.75 0.75 0.75 0.75 Zinc carbonate *4 1.6 1.6 1.6 — 1.6 SeleniumDisulfide *5 1.0 0.5 1.0 1.0 1.0 Sulfur *6 — — — — —Stearamidopropyldimeth- 2.0 — — — — ylamine 1-glutamic acid 0.64 — — — —Behenyl trimethyl — 1.8 1.8 1.8 1.8 ammonium methosulfate Dicetyldimethyl — 0.52 0.52 0.52 0.52 ammonium chloride Cetyl alcohol 2.5 1.11.1 1.1 1.1 Stearyl alcohol 4.5 2.75 2.75 2.75 2.75 Polydimethylsiloxane*7 0.6 — — — — Aminosilicone *8 — 0.75 0.75 0.75 0.75 Preservatives 0.450.4 0.4 0.4 0.4 Perfume 0.5 0.5 0.5 0.5 0.5 Malodor Reducing 0.125 0.10.25 0.175 — Composition Deionized Water q.s. to 100% Method ofpreparation I II I II I *1 Polyquaternium-6:Poly(diallyldimethylammonium chloride) supplied with a tradename Merquat100 from Lubrizol, having a charge density of about 6.2 meq/g, andmolecular weight of about 150,000 g/mol *2 Polyquaternium-6:Poly(diallyldimethylammonium chloride) supplied with a tradename Merquat106 from Lubrizol having a charge density of about 6.2 meq/g, andmolecular weight of about 15,000 g/mol *3 Zinc pyrithione: having aparticle size of from about 1 to about 10 microns *4 Zinc carbonate:having a particle size of from about 1 to about 10 microns *5 SeleniumDisulfide, from Eskay *6 Sulfur, from Universal Preserv-A-Chem *7Polydimethylsiloxane: having a viscosity of 10,000 cSt *8 Aminosilicone:Terminal aminosilicone which is available from GE having a viscosity ofabout 10,000 mPa · s, and having following formula:(R₁)_(a)G_(3−a)—Si—(—OSiG₂)_(n)—O—SiG_(3−a)(R₁)_(a) wherein G is methyl;a is an integer of 1; n is a number from 400 to about 600; R₁ is amonovalent radical conforming to the general formula C_(q)H_(2q)L,wherein q is an integer of 3 and L is —NH₂.

Components Ex. 6 Ex. 7 Ex. 8 Polyquaternium-6 *1 — — — Polyquaternium-6*2 0.075 0.075 0.075 Zinc pyrithione *3 0.75 0.75 0.75 Zinc carbonate *41.6 1.6 1.6 Selenium Disulfide *5 1.0 0.1 — Sulfur *6 3.5 2.0 2.0Stearamidopropyldimethylamine — — — 1-glutamic acid — — — Behenyltrimethyl 1.8 1.8 1.8 ammonium methosulfate Dicetyl dimethyl 0.52 0.520.52 ammonium chloride Cetyl alcohol 1.1 1.1 1.1 Stearyl alcohol 2.752.75 2.75 Polydimethylsiloxane *7 — — — Aminosilicone *8 0.75 0.75 0.75Preservatives 0.4 0.4 0.4 Perfume 0.5 0.5 0.5 Malodor Reducing 0.1750.25 0.25 Composition Deionized Water QS to 100% Method of preparationII II II *1 Polyquaternium-6: Poly(diallyldimethylammonium chloride)supplied with a tradename Merquat 100 from Lubrizol, having a chargedensity of about 6.2 meq/g, and molecular weight of about 150,000 g/mol*2 Polyquaternium-6: Poly(diallyldimethylammonium chloride) suppliedwith a tradename Merquat 106 from Lubrizol having a charge density ofabout 6.2 meq/g, and molecular weight of about 15,000 g/mol *3 Zincpyrithione: having a particle size of from about 1 to about 10 microns*4 Zinc carbonate: having a particle size of from about 1 to about 10microns *5 Selenium Disulfide, from Eskay *6 Sulfur, from UniversalPreserv-A-Chem *7 Polydimethylsiloxane: having a viscosity of 10,000 cSt*8 Aminosilicone: Terminal aminosilicone which is available from GEhaving a viscosity of about 10,000 mPa · s, and having followingformula: (R₁)_(a)G_(3−a)—Si—(—OSiG₂)_(n)—O—SiG_(3−a)(R₁)_(a) wherein Gis methyl; a is an integer of 1; n is a number from 400 to about 600; R₁is a monovalent radical conforming to the general formula C_(q)H_(2q)L,wherein q is an integer of 3 and L is —NH₂.Method of Preparation

The conditioning compositions of “Ex. 1” through “Ex.3” and “CEx. i asshown above can be prepared by any conventional method well known in theart. They are suitably made by one of the following Methods I or II asshown above.

Method I

Cationic surfactants and high melting point fatty compounds are added towater with agitation, and heated to about 80° C. The mixture is cooleddown to about 55° C. and gel matrix is formed. Zinc carbonates, and ifincluded, silicones and preservatives, are added to the gel matrix withagitation. Then, zinc pyrithione, and if included, polymers are addedwith agitation at about 45° C. Then, if included, other components suchas perfumes are added with agitation. Then the composition is cooleddown to room temperature.

Method II

Cationic surfactants and high melting point fatty compounds are mixedand heated to from about 66° C. to about 85° C. to form an oil phase.Separately, water is heated to from about 20° C. to about 48° C. to forman aqueous phase. In Becomix® direct injection rotor-stator homogenizer,the oil phase is injected and it takes 0.2 second or less for the oilsphase to reach to a high shear field having an energy density of from1.0×10⁵ J/m³ to 1.0×10⁷ J/m³ where the aqueous phase is already present.A gel matrix is formed at a temperature of above 50° C. to about 60° C.Silicones, Perfume, Polymer and Preservative, if included, are added tothe gel matrix with agitation at temperature below 55° C. and mixedwell. Then, zinc carbonate, if included, followed by zinc pyrithione,are added to the gel matrix with agitation at temperature below 50° C.and mix well. Finally the composition is cooled down to roomtemperature.

Leave on Treatment Formulations and Examples

-   -   The following are non-limiting examples of the present        invention. The examples are given solely for the purpose of        illustration and are not to be construed as limitations of the        present invention, as many variations thereof are possible        without departing from the spirit and scope of the invention,        which would be recognized by one of ordinary skill in the art.

Leave on Treatment Examples

Examples 1 2 3 4 5 6 Active wt Active wt Active wt Active wt Active wtActive wt % % % % % % Water Q.S. Q.S. Q.S. Q.S. Q.S. Q.S. Alcohol 100%50 0 50 0 50 0 (Ethanol) Isoproryl Alcohol 0 0 0 0 0 0 Acrylates/C10-300.35 0.2 0.35 0.2 0.35 0.2 alkyl acrylate crosspolymer *1 Zincpyrithione *2 0.1 0.07 — — — — Selenium Sulfide 0.1 0.1 — — 0.1 0.1 *3Sulfur *4 — — 2.0 2.0 2.0 2.0 Panthenol 0.15 0 0.15 0 0.15 0 Niacinamide2.5 0 2.5 0 2.5 0 Caffeine 0.75 0 0.75 0 0.75 0 Glycerin 0.5 0 0.5 0 0.50 Propylene Glycol 0 1 0 1 0 1 Menthol 0 0.5 0 0.5 0 0.5 Tapicoa Starch0 1 0 1 0 1 Polymethylsilsesuioxane *5 Benzyl Alcohol 0.12 0.5 0.12 0.50.12 0.5 Methylisothiazolinone 0 0.05 0 0.05 0 0.05 *6 PEG-40 0 0.5 00.5 0 0.5 Hydrogenated Castor Oil *7 Tetrahydroxypropyl 0.12 0.14 0.120.14 0.12 0.14 Ethylenediamine *8 Fragrance 0.4 0.2 0.4 0.2 0.4 0.2Malodor Reducing 0.15 0.1 0.15 0.1 0.15 0.1 Composition *1 as inCarbopol Ultrez 21 available from Lubrizol *2 as in ZPT from LonzaPersonal Care *3 as in selenium sulfide from Eskay *4 as in Sulfur, fromUniversal Preserv-A-Chem *5 as in Neolone 950 from Rohm and Haas *6 asin Cremophor RH-40 Surfactant from BASF *7 as in Neutrol Te from BASF *8as in Trolamine from Dow Chemical

In the examples, all concentrations are listed as weight percent, unlessotherwise specified and may exclude minor materials such as diluents,filler, and so forth. The listed formulations, therefore, comprise thelisted components and any minor materials associated with suchcomponents. As is apparent to one of ordinary skill in the art, theselection of these minors will vary depending on the physical andchemical characteristics of the particular ingredients selected to makethe hair care composition

Examples/Combinations

A. A hair care composition comprising, based on total compositionweight,

-   -   a) a sum total of from about 0.0001% to about 2% of        alpha,alpha,6,6-tetramethyl bicyclo[3.1.1]hept-2-ene-propanal)        and one or more malodor reduction materials having a Sulfur        MORV>3;    -   b) from about 0.01% to about 10% of a scalp active material        selected from the group consisting of selenium sulfide, sulfur        and mixtures thereof;    -   c) from about 0.1% to about 40%, of a surfactant.        B. The composition according to Paragraph A, wherein the malodor        reduction materials are selected from the group consisting of        2′-isopropyl-1,7,7-trimethylspiro[bicyclo[2.2.1]heptane-2,4′-[1,3]dioxane],        1′,1′,5′,5′-tetramethylhexahydro-2′H,5′H-spiro[[1,3]dioxolane-2,8′-[2,4a]methanonaphthalene,        3a,4,5,6,7,7a-hexahydro-1H-4,7-methanoinden-6-yl acetate,        3a,4,5,6,7,7a-hexahydro-1H-4,7-methanoinden-6-yl acetate,        (3R,3aR,6S,7S,8aS)-6-methoxy-3,6,8,8-tetramethyloctahydro-1H-3a,7-methanoazulene,        Ethyl        (1R,2R,3R,4R)-3-isopropylbicyclo[2.2.1]hept-5-ene-2-carboxylate),        (3aR,5aR,9aR,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan),        alpha,alpha,6,6-tetramethylbicyclo[3.1.1]hept-2-ene-propanal,        4,5-epoxy-4,11,11-trimethyl-8-methylenebicyclo(7.2.0)undecane),        (4aR,8aS)-7-methyloctahydro-1,4-methanonaphthalen-6(2H)-one),        (5-methoxyoctahydro-1H-4,7-methanoindene-2-carbaldehyde),        (2R,4a′R,8a′R)-3,7′-dimethyl-3′,4′,4a′,5′,8′,8a′-hexahydro-1′H-spiro[oxirane-2,2′-[1,4]methanonaphthalene]),        2,2,6,6,7,8,8-heptamethyldecahydro-2H-indeno[4,5-b]furan,        1,3,4,6,7,8alpha-hexahydro-1,1,5,5-tetramethyl-2H-2,4alpha-methanophtalen-8(5H)-one,        (3a,4,5,6,7,7a-hexahydro-1H-4,7-methanoinden-5-yl isobutyrate),        (3S,5aR,7aS,11 aS, 11        bR)-3,8,8,11a-tetramethyldodecahydro-5H-3,5a-epoxynaphtho[2,1-c]oxepine),        8,8-dimethyl-3a,4,5,6,7,7a-hexahydro-1H-4,7-methanoinden-6-yl        propionate,        (4aR,5R,7aS,9R)-2,2,5,8,8,9a-hexamethyloctahydro-4H-4a,9-methanoazuleno[5,6-d][l        1,3]dioxole),        2-(8-isopropyl-6-methylbicyclo[2.2.2]oct-5-en-2-yl)-1,3-dioxolane),        3a,4,5,6,7,7a-hexahydro-1H-4,7-methanoinden-6-yl pivalate,        (3a,5,6,7,8,8b-hexahydro-2,2,6,6,7,8,8-heptamethyl-4H-indeno(4,5-d)-1,3-dioxole),        (3R,3aS,6R,7R,8aS)-3,6,8,8-tetramethyloctahydro-1H-3a,7-methanoazulen-3-yl        formate        (3R,3aS,6R,7R,8aS)-3,6,8,8-tetramethyloctahydro-1H-3a,7-methanoazulen-6-ol,        (1-((2S,3S)-2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)ethan-1-one),        ((E)-4-((3aS,7aS)-octahydro-5H-4,7-methanoinden-5-ylidene)butanal),        (Z)-4,11,11-trimethyl-8-methylenebicyclo[7.2.0]undec-3-en-5-yl        acetate,        (1aR,4S,4aS,7R,7aS,7bS)-1,1,4,7-tetramethyldecahydro-1H-cyclopropa[e]azulen-4-ol),        ((Z)-6-ethylideneoctahydro-2H-5,8-methanochromen-2-one),        1-((3R,3aR,7R,8aS)-3,6,8,8-tetramethyl-2,3,4,7,8,8a-hexahydro-1H-3a,7-methanoazulen-5-yl)ethan-1-one),        3,5,5,6,7,8,8-heptamethyl-5,6,7,8-tetrahydronaphthalene-2-carbonitrile,        2-(cyclohexyloxy)-1,7,7-trimethylbicyclo[2.2.1]heptane        (E)-4-((3aR,4R,7R,7aR)-1,3a,4,6,7,7a-hexahydro-5H-4,7-methanoinden-5-ylidene)-3-methylbutan-2-ol),        ((E)-3,7-dimethylocta-2,6-dien-1-yl palmitate) and mixtures        thereof.        C. The composition according to paragraph according to A-B,        wherein malodor reduction material has a C log P>3.        D. The composition according to paragraph according to A-C,        wherein the malodor reduction material has a VP>0.005.        E. The composition according to paragraph A-D, wherein the        malodor reduction material has a MORV>3, a C log P>3 and a        VP>0.005.        F. The composition according to paragraph A-E, wherein the        malodor reduction material is selected from the group consisting        of        2′-isopropyl-1,7,7-trimethylspiro[bicyclo[2.2.1]heptane-2,4′-[1,3]dioxane,        1′,1′,5′,5′-tetramethylhexahydro-2′H,5′H-spiro[[1,3]dioxolane-2,8′-[2,4a]methanonaphthalene]        K, SPIRO[FURAN-2(3H),5′-(4,7-METHANO-5H-INDENE], DECAHYDRO,        (3R,3aR,6S,7S,8aS)-6-methoxy-3,6,8,8-tetramethyloctahydro-1H-3a,7-methanoazulene,        Ethyl        (1R,2R,3R,4R)-3-isopropylbicyclo[2.2.1]hept-5-ene-2-carboxylate,        3aR,5aR,9aR,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan,        alpha,alpha,6,6-tetramethylbicyclo[3.1.1]hept-2-ene-propanal,        4,5-epoxy-4,11,1-trimethyl-8-methylenebicyclo(7.2.0)undecane,        2′-isopropyl-1,7,7-trimethylspiro[bicyclo[2.2.1]heptane-2,4′-[1,3]dioxane        and mixtures thereof.        G. The composition according to paragraph A-F, wherein the        surfactant is selected from the group consisting of anionic,        amphoteric or zwitterionic, cationic or mixtures thereof.        H. The composition according to paragraph A-G, wherein the        composition comprises the sum total of from about 0.001% to        about 0.75% of the malodor reduction material.        I. The composition according to paragraph A-H, wherein the        composition comprises the sum total of from about 0.01% to about        0.5% of the malodor reduction material.        J. The composition according to paragraph A-I, wherein the        composition comprising one or more perfume raw materials.        K. The composition according to paragraph A-J, wherein a method        of controlling malodors comprising: contacting a situs        comprising a malodor and/or a situs that will become malodorous        with a hair care composition selected from the group consisting        of the hair care composition of paragraph A-J.        L. The composition according to A-K, wherein said situs is a        head of hair and said contacting step comprises contacting said        head of hair with a sufficient amount of a hair care composition        to provide said hair with a level of malodor reduction material        at least 0.0001 mg of malodor reduction material per head of        hair.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application is hereby incorporated herein by reference in itsentirety unless expressly excluded or otherwise limited. The citation ofany document is not an admission that it is prior art with respect toany invention disclosed or claimed herein or that it alone, or in anycombination with any other reference or references, teaches, suggests,or discloses any such invention. Further, to the extent that any meaningor definition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is, therefore,intended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed:
 1. A hair care composition comprising, based on totalcomposition weight, a) a sum total of from about 0.0001% to about 2% ofa malodor reduction material consisting ofalpha,alpha,6,6-tetramethylbicyclo[3.1.1]hept-2-ene-propanal) andmalodor reduction materials2′-isopropyl-1,7,7-trimethylspiro[bicyclo[2.2.1]heptane-2,4′-[1,3]dioxane,1′,1′,5′,5′-tetramethylhexahydro-2′H,5′H-spiro[[1,3]dioxolane-2,8′-[2,4a]methanonaphthalene]K, SPIRO[FURAN-2(3H),5′-(4,7-METHANO-5H-INDENE], DECAHYDRO,(3R,3aR,6S,7S,8aS)-6-methoxy-3,6,8,8-tetramethyloctahydro-1H-3a,7-methanoazulene,Ethyl (1R,2R,3R,4R)-3-isopropylbicyclo[2.2.1]hept-5-ene-2-carboxylate,(3aR,5aR,9aR,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan,bicyclo[3.1.1]hept-2-ene-propanal,4,5-epoxy-4,11,11-trimethyl-8-methylenebicyclo(7.2.0)undecane, and2′-isopropyl-1,7,7-trimethylspiro[bicyclo[2.2.1]heptane-2,4′-[1,3]dioxane;b) from about 0.01% to about 10% of a scalp active material wherein thescalp active material is coal tar; c) from about 0.1% to about 40%, ofan anionic surfactant.
 2. A hair care composition according to claim 1wherein the composition comprises the sum total of from about 0.001% toabout 0.75% of the malodor reduction material.
 3. A hair carecomposition according to claim 1 wherein the composition comprises thesum total of from about 0.01% to about 0.5% of the malodor reductionmaterial.
 4. A hair care composition according claim 1, the compositioncomprising one or more perfume raw materials.
 5. A method of controllingmalodors comprising: contacting a situs comprising a malodor and/or asitus that will become malodorous with the hair care composition ofclaim
 1. 6. The method of claim 5 wherein, said situs is a head of hairand said contacting step comprises contacting said head of hair with asufficient amount of the hair care composition to provide said hair witha level of malodor reduction material at least 0.0001 mg of malodorreduction material per head of hair.